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EP0292433B1 - Composés cationiques - Google Patents

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Publication number
EP0292433B1
EP0292433B1 EP88810307A EP88810307A EP0292433B1 EP 0292433 B1 EP0292433 B1 EP 0292433B1 EP 88810307 A EP88810307 A EP 88810307A EP 88810307 A EP88810307 A EP 88810307A EP 0292433 B1 EP0292433 B1 EP 0292433B1
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Prior art keywords
formula
radical
unsubstituted
cationic compound
c4alkyl
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EP0292433A3 (fr
EP0292433A2 (fr
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Willy Stingelin
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/16—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms
    • C09B23/162—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms
    • C09B23/164—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms containing one nitrogen atom
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents

Definitions

  • the invention relates to new cationic compounds, processes for their preparation and their use for dyeing and printing textile materials, leather and paper.
  • alkyl is generally understood to mean unbranched or branched alkyl groups. It is e.g. methyl, ethyl, n- or iso-propyl, n-, sec- or tert-butyl, straight-chain or branched pentyl or hexyl; also cyclic alkyl groups, e.g. Cyclopentyl, cyclohexyl or methylcyclohexyl.
  • These groups can be substituted, for example, by a C1-C4 alkoxy group such as the methoxy, ethoxy, n and iso-propoxy group or n and iso-butoxy group; by CN, by halogen such as fluorine, chlorine or bromine, by phenyl (in turn optionally further substituted by eg halogen, alkyl and / or alkoxy) by CONH2 or by a mono- or disubstituted on the N atom (eg by C1-C4-alkyl) Carboxamide group.
  • a C1-C4 alkoxy group such as the methoxy, ethoxy, n and iso-propoxy group or n and iso-butoxy group
  • CN by halogen such as fluorine, chlorine or bromine
  • phenyl in turn optionally further substituted by eg halogen, alkyl and / or alkoxy
  • CONH2 a mono- or disubstitute
  • the C1-C4 alkoxy groups are unbranched or branched alkoxy groups such as e.g. around methoxy, ethoxy, n- and iso-propoxy or n- and iso-butoxy, where these groups can be further substituted, for example by phenyl.
  • B or / and B1 is a cationic radical other than Z
  • radicals of the following structures are suitable; and especially residues of the formulas: [-NH (CH2) p -NH (R1) 2] ⁇ , [-N (R1) 3] ⁇ or wherein the substituents R1 and R4 have the meaning given and p is the number 2 or 3.
  • B or B1 in the meaning of a [-NH (CH2) p -N (R1) 3] ⁇ or [-NH (CH2) p -NH (R1) 2] ⁇ group represents for example the following groups:
  • B represents for example one of the following groups: B or / and B1 is a radical of the formula so R5 and R5 are aryl, for example, phenyl or naphthyl.
  • R5 and R6 together with the nitrogen atom to which they are attached form a heterocycle, it is, for example, a 5- or 6-membered heterocycle such as, for example, thiazole , Imidazole, pyrazole, triazole, pyrrolidine, piperazine, piperidine and morpholine.
  • a 5- or 6-membered heterocycle such as, for example, thiazole , Imidazole, pyrazole, triazole, pyrrolidine, piperazine, piperidine and morpholine.
  • Both the aryl radical and the heterocycle can also be substituted, for example by C1-C4-alkoxy, C1-C4-alkyl, OH, halogen (fluorine, chlorine, bromine), NO2, CN, -NH-C1-C4-alkyl, N (alkyl) 2, [ ⁇ N (alkyl) 3] An ⁇ and NH2.
  • this alkyl radical can be interrupted one or more times by -O-, -S- and / or -NH-; this alkyl radical can be unbranched or branched and it can also be substituted.
  • Both the C1-C6 alkyl radical and the C1-C6 alkenyl radical can still be substituted; as substituents are, for example: OH, halogen (fluorine, chlorine, bromine), NO2, CN, NH-alkyl (C1-C4), N (alkyl C1-C4) 2 and [-N (R1) 3] ⁇ .
  • R5 is preferably hydrogen, phenyl or phenyl substituted by C1-C4-alkyl, C1-C4-alkoxy, chlorine, nitro, -NH-C1-C4-alkyl or CN.
  • R6 is preferably hydrogen.
  • dyes of the formula (1) preference is given to those in which B is a Z radical and B 1 is a cationic radical or a radical of the formula
  • B and B 1 each represent a Z radical, and especially those in which the three Z radicals are identical.
  • R3 or R4 is an acylamino group
  • the benzoylamino or acetylamino group can be used.
  • the acylamino group can be substituted by, for example, halogen such as fluorine, chlorine or bromine or by an NH2 group or by an amino group which is mono- or disubstituted on the N atoms by, for example, C1-C4alkyl.
  • R3 or R4 is halogen, it is primarily fluorine, chlorine or bromine.
  • R3 and R4 each independently represent hydrogen or an unsubstituted, unbranched C1-C4 alkyl group, especially the methyl group or an unsubstituted, unbranched C1-C4 alkoxy group, especially the methoxy group, or halogen , especially chlorine.
  • R1, R7 or R8 represents an alkenyl group, it is primarily the allyl group.
  • R1 is an unsubstituted, unbranched C1-C4 alkyl group, especially the CH3 group.
  • X means the -Grouping, wherein the radicals R7 and R8 are linked together to form a carbocyclic 5- or 6-ring, it is primarily the unsubstituted cyclopentane or cyclohexane ring.
  • X means the -Grouping, wherein R7 and R8 each represent an unbranched, unsubstituted C1-C4 alkyl radical; in particular X means the -Grouping.
  • R2 is preferably an unsubstituted C1-C4 alkyl group or benzyl and especially methyl or ethyl.
  • A is an alkylene (C1-C4) -, -NH-alkylene (C1-C4) - or -O-alkylene (C1-C4) bridge, then come as "alkylene” bridges, for example methylene, ethylene, n- and iso-propylene or n- and iso-butylene in question.
  • A is preferably a direct bond, i.e. the Y radical is directly connected to the phenylene radical and the triazine radical.
  • Y in the meaning of a -NR1 group represents an -N-alkyl (C1-C6) group, such as the -N-CH3-, -N-C2H5-, -N-C3H7 group, the alkyl radical still by definition can be substituted, especially by CN or halogen.
  • Y represents the -NH or -NR1 group, in particular the -N-CH3 group.
  • Anions An include both inorganic and organic anions, for example: halides, such as chloride, bromide or iodide, sulfate, methyl sulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, phosphoromolybdate , Phosphotungstamat, Phosphotungstammolybdat-, benzenesulfonate, naphthalenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleinate, formate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or complex anions , like that of double chlorine zinc.
  • halides such as chloride, bromide or iodide, sulfate, methyl sulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, phosphoromolyb
  • Preferred anions are the formate, acetate, lactate, chloride, sulfate and phosphate ion.
  • the new cationic compounds of formula (1) are greenish to reddish yellow compounds. They can be prepared in a manner known per se.
  • the amines of the formulas (5), (8) and (9) are known or can be prepared by methods known per se.
  • the compounds of formula (5) are obtained by mixing 1 mole of s-trichlorotriazine with 3 moles of a compound of the formula implemented, then reduced the NO2 group to the NH2 group in the condensation product and reacted with an alkylating agent introducing the group R2.
  • the compounds of formula (8) are obtained, for example, by s-trichlorotriazine in stages with a compound HB and HB1 to a compound of the formula implements this then with a compound of formula (10) to a compound of formula implemented, then reduced the NO2 group to the NH2 group and condensed with 1 mol of an aldehyde of the formula (6) in the presence of an acid HAn.
  • the compounds of formula (9) are obtained in an analogous manner, for example by first reacting s-trichlorotriazine with 2 moles of a compound of formula (10) and then with 1 mole of a compound BH, then reducing the NO2 group in the condensation product and using an alkylating agent introducing the group R2.
  • the compounds of formula (10) and the aldehydes of formula (6) are also known or can be prepared in a manner known per se.
  • aldehydes of the formula (6) are: 1,3,3-trimethyl-2-methylene-indoline- ⁇ -aldehyde, 1,3,3-trimethyl-5-chloro-2-methylene-indoline- ⁇ -aldehyde, 1,3,3-trimethyl-5-methyl-2-methylene-indoline- ⁇ -aldehyde and 1,3,3-trimethyl-5-cyano-2-methylene-indoline- ⁇ -aldehyde.
  • the condensation reaction of the compounds (5), (8), and (9) with the aldehyde of the formula (6) take place in a known manner, for example in an aqueous medium or organic solvent at a temperature of about 0 ° to 100 ° C.
  • Presence of an acid HAn is an organic acid, such as acetic acid or arylsulfonic acid, especially benzenesulfonic acid, or an inorganic acid, such as hydrochloric acid, sulfuric acid or phosphoric acid.
  • the new cationic compounds are optionally separated from the reaction medium and dried.
  • Another production method for the compounds of the formula (1) consists in starting from compounds which have hydrogen instead of the group R2 and otherwise correspond to the formula (1), and introducing the radical R2 into these compounds.
  • the corresponding starting compounds are known, e.g. from European patent applications 38 299, 94 642 and 145 656.
  • the compounds according to the invention have the advantage that they are stable even at higher pH values. This allows their use in dyeing processes e.g. at pH values up to approx. 9.
  • the anion An can be exchanged for another anion in a known manner in the cationic compounds of the formula (1).
  • the new compounds can also be converted into a liquid commercial form directly after concentration of the reaction medium.
  • the new cationic compounds of the formula (1) are used as dyes for dyeing and, with the addition of binders and, if appropriate, solvents, for printing on materials which can be dyed with cationic dyes, in particular textile materials which consist, for example, of homopolymers or copolymers of acrylonitrile or of synthetic polyamides or polyesters modified by acidic groups. It is preferably dyed in an aqueous, neutral or acidic medium by the exhaust process, if appropriate under pressure, or by the continuous process.
  • the textile material can be in a wide variety of forms, for example as fiber, thread, fabric, knitted fabric, piece goods and finished goods such as shirts or pullovers.
  • the dyes can be used to produce level greenish to rusty yellow tints or prints that are characterized by very good general fastness properties.
  • the new cationic dyes can also be used for dyeing and printing natural and regenerated cellulose materials, especially cotton and viscose, with greenish to reddish yellow colorations.
  • the new dyes have good drawability, a good degree of exhaustion on these textile materials and the dyeings obtained have very good fastness properties, especially wet fastness properties.
  • Another use of the new cationic dyes of the formula (1) is in the application for dyeing paper of all types, especially bleached, unsized lignin-free paper. These compounds are very particularly suitable for dyeing unsized paper (tissues) because of their very high affinity for this substrate.
  • the new compounds absorb very well on these substrates, so that the waste water remains practically colorless.
  • the dyeings obtained are wet-fast, ie they show no tendency to bleed out when colored paper is brought into contact with moist white paper in the wet state. This property is particularly desirable for so-called “tissues”, in which it is foreseeable that the colored paper will come into contact with other surfaces such as textiles, paper and the like when wet (eg soaked with water, alcohol, surfactant solution, etc.), that must be protected against pollution.
  • the new dyes can be applied to the paper material using a variety of processes, e.g. in bulk dyeing, in the size press and from aqueous inks according to the INK-JET method.
  • the new dyes can also be used to dye leather (e.g. by spraying, brushing and dipping) and to prepare inks.
  • the abbreviation RKN represents a quality designation and indicates the degree of purity of the cellulose;
  • Abbreviation SR Schopper-Riegler indicates the degree of grinding.
  • Example 1 9.1 parts of 2,4,6-s-tri- (4'-N-methylaminophenylamino) triazine and 12.0 parts of 1,3,3-trimethyl-2-methyleneindoline- ⁇ -aldehyde are in 60 Parts of methanol and 3.9 parts of 85% formic acid stirred at 20-25 °. The condensation is complete after 10 hours, the methanol is removed by distillation in vacuo, and 22.0 parts of brown dye powder having the following structure are obtained: The dye dyes paper in brilliant greenish yellow.
  • Example 2 The dye cation according to the structure of Example 1 can also be obtained by quaternization with dimethyl sulfate in water of the corresponding dye base, the following structure: The preparation of the color base is described in Example 1 of EP-A-38 299.
  • Examples 3-13 According to the procedure given in Example 1 and using the components listed in the following table, cationic dyes are obtained which dye paper in greenish yellow shades.
  • Example 27 50 parts of chemically bleached beech sulfite pulp are mixed with 50 parts of bleached cellulose RKN 15 (degree of grinding 22 ° SR) and 2 parts of the dye according to Example 1 in water (pH 6, water hardness 10 ° dH, temperature 20 °, Fleet ratio 1:40). After stirring for 15 minutes, paper sheets are produced on a Frank sheet former.
  • the paper is colored in a very intense greenish yellow shade.
  • the waste water is completely colorless.
  • the degree of extension reaches practically 100%.
  • the light and wet fastness properties are excellent.
  • Example 28 A paper web is made from bleached beech sulfite pulp (22 ° SR) on a continuously operating laboratory paper machine. Ten seconds before the headbox, an aqueous solution of the dye according to Example 1 is metered continuously into the thin material under strong turbulence (0.5% color, liquor ratio 1: 400, water hardness 10 ° dH, pH 6, temperature 20 °).
  • a strong yellow shade of medium intensity is created on the paper web.
  • the waste water is completely colorless.
  • Example 29 If dyeing is carried out using the same procedure as in Example 28, but at pH 8.5, an equally colored paper web is obtained, the waste water being completely colorless.
  • Example 30 10 parts of cotton fabric (bleached mercerized cotton) are in a laboratory tree dyeing machine in 200 parts of a liquor (water hardness 10 ° dH, pH 4.3, 3 circulations of the dyeing liquor per minute) which contains 0.05 part of the dye according to Example 1, colored. The temperature is heated from 20 ° to 100 ° in 60 minutes, then kept constant for 15 minutes.
  • a liquor water hardness 10 ° dH, pH 4.3, 3 circulations of the dyeing liquor per minute
  • the dyeing liquor has been completely removed.
  • a strong yellow color is created on the cotton fabric, which is characterized by good light fastness and very good wet fastness.

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Claims (21)

  1. Composés cationiques de formule
    Figure imgb0063
     dans laquelle :
    Z présente un groupe de formule
    Figure imgb0064
     B et B¹ représentent chacun, indépendamment l'un de l'autre, un reste Z, un reste cationique différent de Z ou un reste de formule
    Figure imgb0065
     R¹ représente un groupe alkyle en C₁-C₆ ou alcényle en C₃-C₄, éventuellement substitué,
    R² représente un groupe alkyle en C₁-C₆ éventuellement substitué,
    R³ et R⁴ représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe alkyle en C₁-C₄ éventuellement substitué, un groupe alcoxy en C₁-C₄ éventuellement substitué, un groupe NO₂, un groupe acylamino éventuellement substitué, un atome d'halogène ou un groupe CN,
    R⁵ représente un atome d'hydrogène ou un groupe alkyle en C₁-C₆, alcényle en C₃-C₆ ou aryle, éventuellement substitué,
    R⁶ représente un atome d'hydrogène ou un groupe alkyle en C₁-C₆, alcényle en C₃-C₆ ou aryle, éventuellement substitué, ou bien R⁵ et R⁶, conjointement avec l'atome d'azote qui les relie, forment un groupe hétérocyclique,
    X représente un atome de soufre ou le groupe
    Figure imgb0066
     dans lequel
    R⁷ et R⁸ représentent chacun, indépendamment l'un de l'autre, un groupe alkyle en C₁-C₆ ou alcényle en C₃-C₄, ces groupes R⁷ et R⁸ pouvant également être raccordés l'un à l'autre en un carbocycle de 5 ou 6 chaînons,
    A représente un liaison directe, ou un groupe -NH-alkylène en C₁-C₄, - O-alkylène en C₁-C₄, alkylène en C₁-C₄, phénylène, -O-phénylène ou - NH-phénylène,
    Y représente -NH-, -NR¹-, -O- ou -S-,
    n vaut 1, 2 ou 3 et
    An⁻ représente un anion.
  2. Composés cationiques conformes à la revendication 1, caractérisés en ce que les restes cationiques B et/ou B¹ possèdent l'une des structures suivantes :
    Figure imgb0067
     [ -NH(CH₂)p-NH(R¹)₂ ]⊕ , [ -N(R¹)₃ ]⊕ ou
    Figure imgb0068
     dans lesquelles les substituants R¹ et R⁴ ont les significations indiquées et p représente le nombre 2 ou 3.
  3. Composés cationiques conformes à la revendication 1, caractérisés en ce que B et/ou B¹ représentent un reste de formule
    Figure imgb0069
     dans laquelle, R⁶ représente un atome d'hydrogène et R⁵ représente un atome d'hydrogène, un groupe phényle ou un groupe phényle substitué par alkyle en C₁-C₄, alcoxy en C₁-C₄, chloro, nitro, - NH- alkyle en C₁-C₄ ou -CN.
  4. Composés cationiques conformes à la revendication 1, caractérisés en ce que B et/ou B¹ représentent un reste Z.
  5. Composés cationiques conformes à l'une des revendications 1 à 4, caractérisés en ce R³ et R⁴ représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou d'halogène ou un groupe alkyle ou alcoxy en C₁-C₄ non substitué.
  6. Composés cationiques conformes à la revendication 5, caractérisés en ce que R³ et R⁴ représentent chacun, indépendamment l'un de l'autre, un groupe méthyle, un groupe méthoxy ou un atome de chlore.
  7. Composés cationiques conformes à l'une des revendications 1 à 6, caractérisés en ce que R¹ représente un groupe alkyle en C₁-C₄ non substitué, et surtout un groupe méthyle.
  8. Composés cationiques conformes à l'une des revendications 1 à 7, caractérisés en ce que X représente le groupe
    Figure imgb0070
     dans lequel R⁷ et R⁸ représentent chacun, indépendamment l'un de l'autre, un groupe alkyle en C₁-C₄ non substitué.
  9. Composés cationiques conformes à l'une de revendications 1 à 8, caractérisés en ce que R⁷ et R⁸ représentent des groupes méthyle.
  10. Composés cationiques conformes à l'une des revendications 1 à 9, caractérisés en ce que R² représente un groupe alkyle en C₁-C₄ ou benzyle, non substitué.
  11. Composés cationiques conformes à l'une des revendications 1 à 10, caractérisés en ce que A représente une liaison directe ou un groupe -O-phénylène ou -NH-phénylène.
  12. Composés cationiques conformes à la revendication 11, caractérisés en ce que A représente une liaison directe.
  13. Composés cationiques conformes à l'une des revendications 1 à 12, caractérisés en ce que Y représente un groupe -NH- ou -NR¹-.
  14. Composés cationiques conformes à l'une des revendications 1 à 13, caractérisés en ce que An représente un ion formiate, acétate, lactate, chlorure, sulfate ou phosphate.
  15. Composés cationiques de formule
    Figure imgb0071
     dans laquelle :
    Z représente un reste de formule
    Figure imgb0072
     B représente un reste Z ou un reste de formule
    Figure imgb0073
     les R¹ représentent, indépendamment l'un de l'autre, des groupes alkyle en C₁-C₄ non substitué,
    R² représente un groupe alkyle en C₁-C₄ ou benzyle, non substitué,
    R³ et R⁴ représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou de chlore ou un groupe alkyle en C₁-C₄ ou alcoxy en C₁-C₄,
    R⁵ représente un atome d'hydrogène, un groupe phényle ou un groupe phényle substitué par alkyle en C₁-C₄, alcoxy en C₁-C₄, chloro, nitro, -NH-alkyle en C₁-C₄, ou -CN,
    R⁶ représente un atome d'hydrogène ou un groupe alkyle en C₁-C₄ non substitué,
    Y représente -NH- ou -NR¹-
    n vaut 2 ou 3 et
    An⁻ représente un anion.
  16. Procédé de préparation de composés cationiques de formule (1) conformes à la revendication 1, caractérisé en ce que l'on condense une mole d'un composé de formule
    Figure imgb0074
     avec 1 à 3 moles d'un aldéhyde de formule
    Figure imgb0075
     en présence d'un acide HAn, ou bien l'on condense 1 mole d'un composé de formule
    Figure imgb0076
     avec 1 mole d'un aldéhyde de formule (6), en présence d'un acide HAn, ou bien l'on condense 1 mole d'un composé de formule
    Figure imgb0077
     avec 2 moles d'un aldéhyde de formule (6), en présence d'un acide HAn, R¹, R², R³, R⁴, R⁵, R⁶, B, B¹, A, Y et An ayant les significations indiquées à propos de la formule (I).
  17. Procédé conforme à la revendication 16, caractérisé en ce que l'on fait réagir 1 mole d'un composé de formule (5) avec 2,5 à 2,99 moles, et en particulier de 2,8 à 2,99 moles, d'un aldéhyde de formule (6).
  18. Utilisation des composés cationiques de formule (I) conformes à la revendication 1, ou des composés cationiques obtenus conformément à la revendication 16, en tant que colorants pour la teinture et l'impression de matériaux textiles, cuirs et papiers de toutes sortes.
  19. Utilisation conforme à la revendication 18, pour la teinture et l'impression de matériaux en polyacrylonitrile ou de matériaux en polyester ou en polyamide modifiés par un acide, ou encore de matériaux en cellulose naturelle ou régénérée.
  20. Utilisation conforme à la revendication 19 pour la teinture et l'impression de papier exempt de lignine, blanchi et non encollé.
  21. Matériau traité, c'est-à-dire teint ou imprimé, avec les composés cationiques conformes à la revendication 1.
EP88810307A 1987-05-20 1988-05-11 Composés cationiques Expired - Lifetime EP0292433B1 (fr)

Applications Claiming Priority (2)

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CH1941/87 1987-05-20
CH194187 1987-05-20

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EP0292433A2 EP0292433A2 (fr) 1988-11-23
EP0292433A3 EP0292433A3 (fr) 1991-08-07
EP0292433B1 true EP0292433B1 (fr) 1994-05-18

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US (1) US5010190A (fr)
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JP (1) JPS63307876A (fr)
DE (1) DE3889583D1 (fr)
ES (1) ES2053799T3 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2945028A1 (de) * 1979-11-08 1981-05-21 Hoechst Ag, 6000 Frankfurt Quartaere und basische azamethinverbindungen, verfahren zu ihrer herstellung und ihre verwendung als farbmittel
EP0038299B1 (fr) * 1980-04-10 1984-11-14 Ciba-Geigy Ag Composés cationiques
US4439204A (en) * 1981-09-11 1984-03-27 Ciba-Geigy Corporation Dye salts
US4462805A (en) * 1982-05-17 1984-07-31 Ciba-Geigy Corporation Mixture of cationic compounds for dyeing and printing textiles, leather and paper
DE3301025A1 (de) * 1983-01-14 1984-07-19 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von kationischen methinfarbstoffen
US4652645A (en) * 1983-11-16 1987-03-24 Ciba-Geigy Corporation Cationic compounds

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ES2053799T3 (es) 1994-08-01
JPS63307876A (ja) 1988-12-15
DE3889583D1 (de) 1994-06-23
EP0292433A3 (fr) 1991-08-07
EP0292433A2 (fr) 1988-11-23

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